JP6994584B2 - Surface coating film and surface coating fiber reinforced resin molded product and its manufacturing method - Google Patents

Description

The present invention relates to a surface coating film, a surface coated fiber reinforced resin molded product, and a method for producing the same.

In recent years, fiber reinforced plastic molded products have been widely proposed as parts for sports equipment, automobiles, ships, aircraft, etc. that are subject to large impacts and deformation stresses, and are actively adopted especially in fields where lightweight and high mechanical properties are required. Has been done. For example, a carbon fiber reinforced resin molded product is made by impregnating carbon fibers with a resin constituting a fiber-impregnated resin such as a thermoplastic resin or a thermosetting resin (hereinafter, also referred to as “matrix resin”) and curing as necessary. Manufactured by letting it. Since the carbon fiber reinforced resin molded product manufactured in this manner is reinforced with carbon fibers, its physical properties are remarkably improved, and it becomes a lightweight yet tough member.

In the above-mentioned fiber-reinforced resin molded product, the surface of the fiber-reinforced resin molded product has irregularities reflecting the texture or stitches of woven fabric, knitting, etc., and it is difficult to obtain a smooth surface.
As a technique capable of obtaining a fiber reinforced plastic member having a smooth surface without impairing the characteristics of the fiber reinforced plastic as being lightweight, for example, the following component [A] reinforced fiber woven or knitted and thermosetting It contains a fiber reinforced plastic containing a resin, [B] a low elastic modulus surface layer having a tensile modulus of 0.1 to 500 MPa, and [C] a high elastic modulus surface layer having a tensile modulus of 1000 to 30,000 MPa. A fiber reinforced plastic member is disclosed in which a component [C] is disposed via a component [B] on at least one surface of [A] (see, for example, Patent Document 1).
Further, as a method for efficiently obtaining a thermoplastic carbon fiber composite material having good adhesion, concealing carbon fiber grain, and improved design, for example, when the surface temperature is 120 ° C. or higher and 180 ° C. or lower. A thermoplastic carbon fiber having a film, which comprises a step of obtaining a molded product made of a thermoplastic carbon fiber composite material using a certain mold, and 2) a film forming step of forming a film on the surface of the obtained molded product. In the method for producing a composite material, the step of obtaining a molded product in 1) is heat press molding, and in the film forming step of 2), an initiator having a half-life at 140 ° C. of 1 second or more and 2000 seconds or less is used. A method for producing a thermoplastic carbon fiber composite material having a film, in which the added in-mold coating paint is injected into a mold and cured (see, for example, Patent Document 2) is disclosed.

Japanese Patent No. 4645334 Gazette Japanese Patent No. 5771061

In the fiber-reinforced resin molded product described in Patent Document 1, in order to conceal uneven patterns and colors such as the texture and stitches of fibers, it is necessary to apply an undercoat and then repeatedly apply the coating. Further, since air bubbles are easily mixed in the uneven pattern and the productivity is inferior, further improvement is required in the method for producing the thermoplastic carbon fiber composite material described in Patent Document 2.

The present invention has been made in view of the above, and is a surface coating film having excellent vividness when integrally molded with a fiber impregnated resin, and a surface coating fiber reinforced by integrally molding a surface coating film and a fiber impregnated resin. An object of the present invention is to provide a resin molded product and a method for producing the same.
Another object of the present invention is a surface coating film having excellent gloss when integrally molded with the fiber impregnated resin, and a surface coated fiber reinforced resin molded product obtained by integrally molding the surface coating film and the fiber impregnated resin. And, it is an object to provide the manufacturing method thereof.

As a result of diligent research to solve the above problems, the present inventors have provided a base film B having a specific thickness and an easy-adhesive layer A provided on the base film B. The base film B includes the easy-to-mold layer b1 and the flat layer b2 adjacent to the easy-adhesive layer A, and the storage elasticity of each of the easy-to-mold layer b1 and the flat layer b2 satisfies a specific relationship. Moreover, it has been found that the easy-adhesive layer A has a specific thickness, so that it is excellent in vividness even when integrally molded with the fiber-impregnated resin.

That is, the means for solving the above problems include the following embodiments.
<1> The base film B has an easy-adhesive layer A provided on the base film B, and the base film B has an easy-molding layer b1 adjacent to the easy-adhesive layer A and an easy-adhesive layer b1. It has a flat layer b2, the thickness of the easy-adhesion layer A is 30 nm to 250 nm, the thickness of the base film B is 50 μm to 500 μm, and the easy-molding layer b1 and the flat layer b2 are respectively. A surface coating film for integrally molding with a fiber-impregnated resin that satisfies the following formulas 1 and 2.
3 ≦ Ratio of the storage elastic modulus EHb2 of the flat layer b2 at 150 ° C. to the storage elastic modulus EHb1 of the easily molded layer b1 at 150 ° C. (EHb2 / EHb1) Equation 1
1000 MPa ≦ Storage elastic modulus of the easily molded layer b1 at 23 ° C. ELb1 formula 2
<2> The surface coating film according to <1>, wherein the EHb2 / EHb1 in the formula 1 is 50 or less.
<3> The surface coating film according to <1> or <2>, which further satisfies the following formula 3.
10 MPa ≦ Storage elastic modulus of the easily molded layer b1 at 150 ° C. EHb1 ≦ 950 MPa Formula 3
<4> The surface coating film according to any one of <1> to <3>, wherein the base film B is a biaxially oriented film.
<5> The surface coating film according to any one of <1> to <4>, wherein the easily molded layer b1 and the flat layer b2 contain a thermoplastic resin.
<6> The easy-adhesion layer A includes a binder resin and
A cross-linking agent having at least one functional group selected from the group consisting of an epoxy group, an oxazoline group, a silanol group and an isocyanate group.
The surface coating film according to any one of <1> to <5>, which comprises a cured product of the binder resin and the cross-linking agent.
<7> The surface coating film according to any one of <1> to <6>, wherein the total light transmittance with respect to visible light is 80% or more.
<8> A surface-coated fiber-reinforced resin molded product in which a surface-coated film and a fiber-impregnated resin are integrally molded into any one of <1> to <7>.
<9> The surface-coated fiber-reinforced resin molded product according to <8>, wherein the fiber-impregnated resin contains carbon fibers.
<10> Surface-coated fiber-reinforced resin molding comprising a step of contacting and integrally molding the easy-adhesion layer A and the fiber-impregnated resin in the surface-coating film according to any one of <1> to <7>. How to manufacture the product.
<11> The method for producing a surface-coated fiber-reinforced resin molded product according to <10>, wherein the above step is a step of integrally molding the fiber-impregnated resin at 150 ° C. for 10 minutes or less.

According to one embodiment of the present invention, a surface coating film having excellent vividness when integrally molded with a fiber impregnated resin, and a surface coating fiber reinforced resin in which the surface coating film and the fiber impregnated resin are integrally molded. A molded product and a method for manufacturing the same are provided.
Further, according to another embodiment of the present invention, a surface coating film having excellent gloss when integrally molded with the fiber impregnated resin, and a surface coating fiber reinforced by integrally molding the surface coating film and the fiber impregnated resin. A resin molded product and a method for producing the same are provided.

It is a schematic diagram of the structure of the surface-coated fiber reinforced resin molded article which is one aspect of this invention.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In addition, in this specification, "-" indicating a numerical range is used in the sense that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.
Further, in the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, "(meth) acrylic" is a term used in a concept that includes both acrylic and methacrylic, and "(meth) acryloyl" is a term that is used as a concept that includes both acryloyl and methacrylic. Is.
In addition, the term "process" in the present specification is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term "process" will be used as long as the intended purpose of the process is achieved. included.
Further, in the present invention, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Unless otherwise specified, in the present invention, each component in the composition or each structural unit in the polymer may be contained alone or in combination of two or more. ..
Further, in the present invention, the amount of each component in the composition or each structural unit in the polymer has a plurality of substances or structural units corresponding to each component or each structural unit in the polymer in the composition. In the case, unless otherwise specified, it means the total amount of each of the plurality of applicable substances present in the composition or the plurality of applicable constituent units present in the polymer.
Further, in the present invention, a combination of two or more preferred embodiments is a more preferred embodiment.
In the present specification, "brightness" means the reflection of a fluorescent lamp projected on the surface of a surface coating film by visually observing the surface of the surface coating film under a fluorescent lamp in an integrally molded product of a fiber-impregnated resin and a surface coating film. It can be evaluated by the distortion of the image. The clearer the details such as the outline and shape of the reflected image of the fluorescent lamp are, the better the vividness is.
In the present specification, "gloss" refers to a 60 ° gloss value (hereinafter, also referred to as "glossiness / 60 °") on the surface of the surface coating film in an integrally molded product of the fiber impregnated resin and the surface coating film. It can be evaluated by measuring. Further, the higher the glossiness / 60 ° value, the better the glossiness.
Hereinafter, the surface-coated film, the surface-coated fiber-reinforced resin molded product, and the manufacturing method thereof according to the present invention will be described.

(Surface coating film)
The surface coating film for integrally molding with the fiber-impregnated resin according to the present invention includes the base film B and the base film B.
It has an easy-adhesive layer A provided on the base film B, and has.
The base film B has an easy-molding layer b1 and a flat layer b2 adjacent to the easy-adhesive layer A.
The thickness of the easy-adhesion layer A is 30 nm to 250 nm, and the thickness is 30 nm to 250 nm.
The thickness of the base film B is 50 μm to 500 μm.
The easily molded layer b1 and the flat layer b2 satisfy the following formulas 1 and 2, respectively.

3 ≦ Ratio of the storage elastic modulus EHb2 of the flat layer b2 at 150 ° C. to the storage elastic modulus EHb1 of the easily molded layer b1 at 150 ° C. (EHb2 / EHb1) Equation 1
1000 MPa ≦ Storage elastic modulus of the easily molded layer b1 at 23 ° C. ELb1 formula 2

As a result of diligent studies by the present inventors, a surface coating film having excellent vividness (hereinafter, also simply referred to as “vividness”) when integrally molded with the fiber-impregnated resin can be obtained by adopting the above configuration. I found that. Further, when a surface-coated fiber-reinforced resin molded product is molded using this surface-coated film and a fiber-impregnated resin described later, it can be integrally molded with good productivity, and the design and surface can be formed without painting. It has been found that a surface-coated fiber-reinforced resin molded product that can be flattened can be obtained.
The detailed mechanism by which the above effect is obtained is unknown, but it is presumed as follows.

When the fiber-impregnated resin is surface-processed, the curing shrinkage of the resin (matrix resin) constituting the fiber-impregnated resin and / or the difference in thermal expansion between the matrix resin and the fiber (hereinafter, also referred to as "sink of the fiber-impregnated resin"). ) Etc., there is a concern that unevenness may occur on the surface. For surface treatment of unevenness, polishing, putting putty, surfacer application, etc. are performed to correct the unevenness, and as a surface finish, an easy-adhesive film, a rigid film, etc. are laminated to impart designability and durability. .. In the fiber-impregnated resin and the integrally molded product obtained by such surface treatment, the interfacial reflection between the fiber-impregnated resin and the easy-adhesive film remains, and the reflected image looks distorted. Therefore, improvement in the vividness is required.
When the easy-to-mold layer b1 constituting the base film B exhibits a storage elastic modulus of 23 ° C. above a specific value, the present inventors have the easy-to-mold layer b1 with appropriate flexibility and hardness. Moreover, it has been found that the adhesion to the easy-adhesion layer A is excellent, and the surface coating film containing these is excellent in vividness.
Further, by setting the ratio of the storage elastic modulus of the easy-molding layer b1 and the flat layer b2 to the range specified by the above formula 1 at 150 ° C., the matrix resin is cured when the above-mentioned fiber-impregnated resin is integrally molded. By having the flat layer b2 while alleviating the deformation due to the shrinkage or the difference in thermal expansion by the easy-molding layer b1, the influence of the unevenness derived from the fiber-impregnated resin due to the deformation of the matrix resin affects the surface shape of the outermost layer. As a result, it is presumed that the surface coating film according to the present invention has excellent vividness.
Further, it is considered that the easy-molding layer b1 having a certain degree of hardness at room temperature makes it easy to handle during integral molding and easily suppresses scratches (hereinafter, also referred to as “scratches”) that enter the surface coating film. Further, it is presumed that the surface coating film according to the present invention has the easy-adhesive layer A, so that the easy-molding layer b1 and the matrix resin can be firmly adhered to each other, and the image quality is excellent.
Hereinafter, each configuration constituting the coating film according to the present invention will be described below.

<Base film B>
The surface coating film according to the present invention has a base film B and an easily adhesive layer A provided on the base film B, and the base film B is easily adjacent to the easy adhesive layer A. It has a molded layer b1 and a flat layer b2, and the thickness of the base film B is 50 μm to 500 μm.
The thickness of the base film B refers to the easy-forming layer b1 adjacent to the easy-adhesive layer A, the flat layer b2, and other layers other than the easy-forming layer b1 and the flat layer b2 provided in some cases (other layers described later). b3) and the total distance in the thickness direction of the multilayer including.
When the thickness of the base film B is in the range of 50 μm to 500 μm, the processability when integrally molded with the fiber-impregnated resin described later is excellent, and the flatness when the surface of the fiber-impregnated resin described later is coated with the surface coating film. Excellent for.
From the above viewpoint, the thickness of the base film B is preferably 75 μm or more, more preferably 100 μm or more, and further preferably 125 μm or more. From the above viewpoint, the thickness of the base film B is preferably 300 μm or less, more preferably 250 μm or less, still more preferably 240 μm or less, still more preferably 188 μm or less, and particularly preferably 130 μm or less. Very preferably less than 100 μm.
Further, as for the thickness of the base film B, the thickness of the base film B can be obtained from the obtained image and scale by observing the cross section of the base film B with a stereomicroscope.

The base film B is a biaxially oriented film in which the molecular chains are oriented by stretching the film in two directions orthogonal to each other in the plane from the viewpoint of achieving both formability and flatness in integral molding. preferable.

-Easy molding layer b1-
The base film B used in the present invention has an easy-adhesive layer A and an easily-molded layer b1 adjacent to the easy-adhesive layer A.
The easily molded layer b1 satisfies the following formula 2. When the easy-molding layer b1 satisfies the formula 2, that is, when the storage elastic modulus ELb1 of the easy-molding layer b1 at 23 ° C. is 1000 MPa or more, the easy-molding layer b1 has an appropriate softness and this appropriate softness. As a result, it is considered that the adhesion to the easy-adhesion layer A, which will be described later, is improved, and the softness and the adhesion are combined to be excellent in the vividness. Further, when the easy-molding layer b1 satisfies the formula 2, the handling at the time of integral molding is good, and it becomes easy to suppress scratches.

1000 MPa ≦ Storage elastic modulus of the easily molded layer b1 at 23 ° C. ELb1 formula 2

From the viewpoint of excellent image quality, the storage elastic modulus ELb1 at 23 ° C. is preferably 2000 MPa or more, preferably 2000 MPa or more and less than 4000 MPa, more preferably 2000 MPa to 3500 MPa, and 2500 MPa to 3000 MPa. It is more preferable to have.

The storage elastic modulus ELb1 of the easy-molding layer b1 at 23 ° C. is obtained by pulling the easy-molding layer b1 in the MD direction with a tension jig using a dynamic viscoelasticity measuring device (product name; DMA8000, manufactured by PerkinElmer Co., Ltd.) at 1 Hz. The storage elastic modulus was measured while raising the temperature at the frequency of. From the measurement results, the storage elastic modulus at 23 ° C. can be obtained.
As used herein, the "MD direction" means the film transport direction (Machine Direction), that is, the longitudinal direction.

From the viewpoint of vividness, the easily molded layer b1 preferably further satisfies the following formula 3.
Storage elastic modulus of 10 MPa ≦ easy-molding layer b1 at 150 ° C. EHb1 ≦ 950 MPa Formula 3
The storage elastic modulus EHb1 of the easy-molding layer b1 at 150 ° C. can be obtained by the same method as the storage elastic modulus ELb1 of the easy-molding layer b1 at 23 ° C.

From the viewpoint of vividness, the storage elastic modulus EHb1 of the easily molded layer b1 at 150 ° C. is preferably 20 MPa to 500 MPa, more preferably 30 MPa to 200 MPa.

The easily molded layer b1 and the flat layer b2 described later satisfy the following formula 1. When the easy-molding layer b1 and the flat layer b2 satisfy the following formula 1, the curing shrinkage and the difference in thermal expansion of the matrix resin can be alleviated in the thickness direction at the processing temperature at the time of integral molding, and the vividness is excellent.

3 ≦ Ratio of the storage elastic modulus EHb2 of the flat layer b2 at 150 ° C. to the storage elastic modulus EHb1 of the easily molded layer b1 at 150 ° C. (EHb2 / EHb1) Equation 1

From the viewpoint of excellent vividness, EHb2 / EHb1 is 3 or more, preferably 6 or more, more preferably 10 or more, and further preferably 20 or more. From the viewpoint of handling, it is preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. Further, from the viewpoint of ensuring a higher degree of vividness and appropriate handleability, EHb2 / EHb1 is preferably in the range of 10 to 45. On the other hand, from the viewpoint of ensuring a high degree of handleability while maintaining a certain degree of vividness, EHb2 / EHb1 is preferably in the range of 3 to 9.
The storage elastic modulus EHb2 of the flat layer b2 at 150 ° C. can be obtained by the same method as the storage elastic modulus ELb1 of the easily molded layer b1 at 23 ° C. described above.

The easily molded layer b1 is preferably a layer containing a thermoplastic resin. As the layer containing the thermoplastic resin, a resin film made of the thermoplastic resin can be preferably used.
The thermoplastic resin used for the easily molded layer b1 may be used alone or in combination of two or more.
The thermoplastic resin is not particularly limited as long as it can be molded into a film or a sheet.
Specific thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, and poly (4-methylpentene-1), ring-opened metathesis polymers of norbornenes, addition polymers, and addition copolymers with other olefins. Cycloolefins such as, biodegradable polymers such as polylactic acid and polybutylsuccinates, polyamide resins such as nylons 6,11,12,66 (including semi-aromatic polyamides), polymethylmethacrylates, polyvinylchlorides, polychlorides, etc. Vinylidene, polyvinyl alcohol, polyvinyl butyral, ethylene vinyl acetate copolymer, polyacetal, polyglycolic acid, polystyrene, styrene copolymer polymethylmethacrylate, polycarbonate, polypropylene terephthalate, polyethylene terephthalate (PET), polyethylene isophthalate (IAPET), polybutylene terephthalate. (PBT), polyester resins such as polyethylene-2,6-naphthalate (PEN), polyether sulfone, polyether ketone, modified polyphenylene ether, polyphenylene sulfide, polyetherimide, polyimide, polyarylate, ethylene tetrafluoride-6 Those known per se, such as a propylene fluoride copolymer, polyvinylidene fluoride, and an acrylic nitrile / butadiene / styrene copolymer copolymer, can be used.

Among these, the thermoplastic resins include polymethylmethacrylate resins, polycarbonate resins, and the like, because when the surface of the fiber-impregnated resin is coated, flatness is more easily developed and transparency that contributes to glossiness is easily imparted. It is preferably at least one resin selected from the group consisting of polyester resins, and more preferably polyester resins because it is easier to provide flatness by stretching or the like.
These resins may be homopolymers, copolymers, or mixtures of thermoplastic resins.

Further, the thermoplastic resin is, for example, an antioxidant, an antioxidant, a crystal nucleating agent, an inorganic particle, an organic particle, a thickener, a heat stabilizer, a lubricant, an infrared absorber, an ultraviolet absorber, and a refractive index adjustment. A thermoplastic resin composition may be prepared by adding an additive such as a doping agent for the purpose.

When a polyester resin is used as the thermoplastic resin, the polyester resin is a monomer synthesized from an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid or an ester-forming derivative thereof, and a diol or an ester-forming derivative thereof. Polyester resins obtained by polymerization are preferably mentioned, and those known per se can be used.

The aromatic dicarboxylic acid is not particularly limited, and is, for example, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4. Examples thereof include'-diphenyldicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 2,5-frangicarboxylic acid, and ester-forming derivatives thereof.
The aliphatic dicarboxylic acid is not particularly limited, and examples thereof include adipic acid, sebacic acid, dimer acid, dodecandioic acid, cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.

Among these, the dicarboxylic acid used for the polyester resin is preferably an aromatic dicarboxylic acid, and is preferably terephthalic acid, isophthalic acid, 2,6- A naphthalenedicarboxylic acid or an ester-forming derivative thereof is more preferable.
Only one kind of these acid components may be used, two or more kinds thereof may be used in combination, and further, these may be partially copolymerized with oxyacid of hydroxybenzoic acid or the like.

Examples of the diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1 , 6-Hexanediol, 1,2-Cyclohexanedimethanol, 1,3-Cyclohexanedimethanol, 1,4-Cyclohexanedimethanol, Diethylene glycol, Triethylene glycol, Polyalkylene glycol, 2,2-Bis (4-hydroxyethoxy) Examples thereof include phenyl) propane, isosorbide, spiroglycol and an ester-forming derivative thereof.
Among these, since it has excellent heat resistance and can have flatness after integral molding, the diol is selected from the group consisting of ethylene glycol, 1,3-butanediol, 1,4-butanediol, and ester-forming derivatives thereof. It is preferably at least one diol of choice.
These diol components may be used alone or in combination of two or more.

When a polyester resin is used as the thermoplastic resin, the polyester resin may be ethylene terephthalate, ethylene isophthalate, ethylene naphthalenedicarboxylate, butylene terephthalate, butylene naphthalene dicarboxylate, from the viewpoint of achieving both moldability and flatness. At least one monomer selected from the group consisting of hexamethylene terephthalate, hexamethylene naphthalenedicarboxylate, 1,4-cyclohexanedimethylene terephthalate, ethylene furanoate and 1,4-cyclohexanedimethylene naphthalenedicarboxylate. A polyester resin having a constituent unit derived from it is preferable, and a polyester resin having a constituent unit derived from at least one monomer selected from the group consisting of ethylene terephthalate, butylene terephthalate and ethylene isophthalate is more preferable.
The polyester resin is not limited to the homopolymer of the monomer, but may be a copolymer using two or more of the monomers, and is a mixture of two or more kinds of polyester resins. You may.
From the viewpoint of formability and vividness at the time of integral molding, the polyester resin is preferably a mixture of two or more kinds of polyester resins, and is at least selected from the group consisting of polyethylene terephthalate, polyethylene isophthalate and polybutylene terephthalate. A mixture containing the two types is more preferable, and a mixture of polyethylene isophthalate and polybutylene terephthalate is further preferable.
From the viewpoint of excellent moldability at the time of integral molding, the polyester resin is preferably a polyester resin having a structural unit derived from at least one selected from the group consisting of butylene terephthalate and ethylene isophthalate.
In particular, since the polyester resin has excellent formability at the time of integral molding, the polyester resin has 80 mol% or more of the constituent units derived from butylene terephthalate and ethylene isophthalate with respect to all the constituent units constituting the polyester resin based on the number of moles. However, a composition unit derived from a monomer other than butylene terephthalate and ethylene isophthalate is copolymerized in an amount of 2 mol% to 20 mol%, which is particularly preferable.

The weight average molecular weight of the thermoplastic resin used for the easily molded layer b1 is preferably 50,000 to 90,000, more preferably 60,000 to 80,000.
The weight average molecular weight can be obtained by the following measuring method.
A sample of thermoplastic resin is freeze-ground, 1 mg of this sample is dissolved overnight in 4 mL of a mixed solvent of hexafluoroisopropanol (HFIP): chloroform = 1: 1, diluted with 6 mL of chloroform, and then with a 0.45 μm membrane filter. It was filtered to obtain a measurement solution.
The measurement solution prepared by the above method was measured by a gel permeation chromatography (GPC) analyzer under the following conditions. The weight average molecular weight was calculated as a conversion value of standard polystyrene.
-Device name: Tosoh Corporation Model number: HLC-8320GPC
-Column: TSK-GEL GMHHR-M (manufactured by Tosoh Corporation) x 2-Flow velocity: 1.0 mL / min
-Column temperature: 40 ° C
・ Detector: UV
・ Injection amount: 200 μL

The easily molded layer b1 may contain a colorant in addition to the above-mentioned thermoplastic resin. Examples of the colorant include colorants used for the decorative layer described later.
The thickness of the easily molded layer b1 is preferably 1 μm or more because it is easy to form a layer having sufficient hardness and strength, more preferably 5 μm or more, further preferably 10 μm or more, and further preferably 25 μm or more. It is preferably 30 μm or more, and particularly preferably 30 μm or more. The thickness of the easily molded layer b1 is preferably 475 μm or less because it is easy to form a layer having the required flexibility, more preferably 470 μm or less, further preferably 350 μm or less, and further preferably 250 μm or less. preferable.

-Flat layer b2-
The base film B used in the present invention has a flat layer b2, and the flat layer b2 satisfies the above formula 1. Further, the flat layer b2 is preferably a layer provided on the above-mentioned easy-molding layer b1, is a layer provided on the easy-molding layer b1, and is adjacent to the easy-molding layer b1. It is more preferably a layer.
When the flat layer b2 is the outermost layer of the surface coating film, it may function as a protective layer.
The flat layer b2 is preferably a layer containing a thermoplastic resin from the viewpoint of maintaining durability while expressing the design of the texture.
The thermoplastic resin used for the flat layer b2 has the same meaning as the thermoplastic resin for the easily molded layer b1 described above.
Polymethylmethacrylate resin and polycarbonate are examples of the thermoplastic resin used for the flat layer b2 because it is easier to develop flatness when the surface of the fiber-impregnated resin is coated and it is easy to impart transparency that contributes to glossiness. At least one resin selected from the group consisting of a resin and a polyester resin is preferable, and a polyester resin is more preferable because it is easier to provide flatness by stretching or the like.
The specific example of the polyester resin used for the flat layer b2 is the same as the specific example of the easy-molding layer b1.

The polyester resin used for the flat layer b2 may be a homopolymer, a copolymer using two or more kinds of monomers, or a mixture of two or more kinds of polyester resins, but alone. It is preferably a polymer or a copolymer, and more preferably a homopolymer.
The homopolymer of the polyester resin is preferably polyethylene terephthalate (PET), polyethylene terephthalate (IAPET), polybutylene terephthalate (PBT) or polyethylene-2,6-naphthalate (PEN), preferably polyethylene terephthalate (PEN). It is more preferably PET) or polyethylene-2,6-naphthalate (PEN).

The thickness of the flat layer b2 is preferably 25 μm to 499 μm, more preferably 25 μm to 495 μm, further preferably 25 μm to 490 μm, further preferably 25 μm to 475 μm, and further preferably 25 μm to 470 μm. Even more preferably, it is particularly preferably 25 μm to 350 μm, and extremely preferably 30 μm to 250 μm.
The thickness of the flat layer b2 can be determined by observing the cross section of the base film B including the easily molded layer b1 and the flat layer b2 with a stereomicroscope and obtaining the thickness of the flat layer b2 from the obtained image and scale.

-Other layers-
The base film B used in the present invention includes layers other than the easily molded layer b1 and the flat layer b2 (hereinafter, "other layers b3") as long as the thickness of the base film B is within the range of 50 μm to 500 μm. However, it is preferable not to have it because forming an unnecessary interface from the viewpoint of exhibiting vividness causes extra reflection.
When the base film B used in the present invention includes another layer b3, the other layer b3 may be a layer containing a resin other than the thermoplastic resin used for the easy-molding layer b1 and the flat layer b2. , More preferably, it may be a layer containing an olefin resin or an acrylic resin.

<Easy adhesive layer A>
The easy-adhesive layer A of the surface coating film according to the present invention has a thickness of 30 nm to 250 nm (0.030 μm to 0.250 μm). Further, in the surface coating film, the easy-adhesive layer A is a layer adjacent to the above-mentioned easy-molding layer b1.
When the thickness of the easy-adhesion layer A is within the above range, the vividness is excellent.
The thickness of the easy-adhesion layer A is preferably 40 nm or more, more preferably 60 nm or more, still more preferably 75 nm or more, from the viewpoint of vividness and adhesion.
The upper limit of the thickness of the easy-adhesion layer A is preferably 180 nm or less, more preferably 150 nm or less, still more preferably 120 nm or less, from the viewpoint of coating thickness, spot reduction, and durable adhesion.

For the thickness of the easy-adhesion layer A, a sample in which the surface coating film according to the present invention was embedded with an epoxy resin was prepared, and after the sample was cured at room temperature for 1 day, a microtome (product name; RM2255, manufactured by Leica Co., Ltd.) was prepared. ) Is used to prepare an ultrathin section, the cross section of the ultrathin section is observed with a TEM (transmission electron microscope), and the thickness of the easy-adhesion layer A can be calculated from the obtained image and scale.

The easy-adhesion layer A has a binder resin and at least one functional group (hereinafter, also referred to as "specific functional group") selected from the group consisting of an epoxy group, an oxazoline group, a melamine group, a silanol group and an isocyanate group. It is preferable to include a cross-linking agent (hereinafter, also referred to as “specific cross-linking agent”) and a cured product of the binder resin and the cross-linking agent. The melamine group is not a formal chemical term, and here, each of the three carbon atoms constituting the triazine ring represented by the 1,3,5-triazine ring has a nitrogen atom (however, nitrogen in the triazine ring). It refers to the so-called melamine skeleton to which (non-atomic) bonds.
Since the easy-adhesive layer A contains a binder resin, a specific cross-linking agent, and a cured product thereof, the adhesiveness between the fiber-impregnated resin described later and the fiber-impregnated resin after integral molding is excellent.

<< Specific cross-linking agent >>
From the viewpoint of adhesion to the fiber-impregnated resin, the specific functional group of the specific cross-linking agent is at least one functional group selected from the group consisting of an isocyanate group, a silanol group, a melamine group, an epoxy group and an oxazoline group. It is preferable to have it, and it is particularly preferable to contain an epoxy group.

From the viewpoint of improving the film-forming property and adhesion to the fiber-impregnated resin when the easy-adhesion layer A is applied on the base film B and increasing the curing rate, the number of functional groups of the specific cross-linking agent is 2. It is preferably more than a functional group. Further, when the curing rate is slowed down, it is preferable to reduce the ratio of the cross-linking agent of the tetrafunctional group in the specific cross-linking agent.

Examples of the cross-linking agent having an isocyanate group include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydride tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, and hexa. Methylene diisocyanate, diphenylmethane-4,4-diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, 1,5-naphthalenediocyanate, triphenylmethane triisocyanate, and their polyisocyanates. Examples thereof include an adduct form of the compound and a polyol compound such as trimethylolpropane, and a biuret form and an isocyanurate form of these polyisocyanate compounds.
Among these, hexamethylene diisocyanate is preferable from the viewpoint of hardness of the cured product and dispersibility of the paint.
Examples of the cross-linking agent having a silanol group include a silane coupling agent represented by the general formula YRSiX ₃ . Here, Y is an organic functional group such as a vinyl group, an epoxy group, an amino group and a mercapto group, R is an alkylene group such as methylene, ethylene and propylene group, and X is a hydrolyzable group such as a methoxy group and an ethoxy group. It is an alkyl group (at least one X in the molecule is a hydrolysis group). It is particularly preferable that the Y moiety is an epoxy group. Specific preferred silane coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and the like. In addition, organometallic compounds containing metals such as zirconium, titanium, and aluminum are preferably classified into alkoxides, chelates, and acylates. Specific examples include, but are not limited to, zirconium tetraacetylacetonate, zirconium acetate, titanium acetylacetonate, triethanolamine titanate, and titanium lactate.
As the compound having a melamine group, a methylol melamine derivative obtained by condensing melamine and formaldehyde, a compound obtained by reacting these with methyl alcohol, ethyl alcohol, isopropyl alcohol or the like as a lower alcohol to etherify them, and a mixture thereof are preferable. Examples of the methylol melamine derivative include monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine and the like.

Examples of the cross-linking agent containing an epoxy group include bisphenol A / epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-. Examples thereof include hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl erythritol, diglycerol polyglycidyl ether and the like.
Among these, glycerol polyglycidyl ether or sorbitol polyglycidyl ether is preferable from the viewpoint of hardness of the cured product and dispersibility of the paint.
As the cross-linking agent having an oxazoline group, a polymer having an oxazoline group is preferable. Such a polymer can be produced by polymerization of an addition-polymerizable oxazoline group-containing monomer alone or with another monomer. Addition-polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-Isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like can be mentioned, and one or a mixture of two or more thereof can be used. Of these, 2-isopropenyl-2-oxazoline is industrially readily available and suitable, and copolymerization at a ratio of the content of the oxazoline group in the polymer to 1 to 10 mmol / g is adhesive. It is preferable from the viewpoint of. The other monomer is not limited as long as it is a monomer copolymerizable with the addition-polymerizable oxazoline group-containing monomer, and is, for example, an alkyl acrylate, an alkyl methacrylate (as the alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc. A (meth) crylic acid esters such as n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group; acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, Unsaturated carboxylic acids such as styrene sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); unsaturated nitriles such as acrylonitrile and methacrylonitrile; acrylamide, methacrylicamide, N-alkyl Acrylamide, N-alkylmethacrylate, N, N-dialkylacrylamide, N, N-dialkylmethacrylate (alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t -Unsaturated amides such as butyl group, 2-ethylhexyl group, cyclohexyl group, etc .; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene Classes; halogen-containing α, β-unsaturated monomers such as vinyl chloride, vinylidene chloride, vinyl fluoride, etc .; α, β-unsaturated aromatic monomers such as styrene, α-methylstyrene, etc. can be mentioned. One or more monomers can be used.

<< Binder resin >>
As the binder resin, any known binder resin can be used as long as it can undergo a cross-linking reaction with the above-mentioned specific cross-linking agent and has excellent adhesion to the above-mentioned base film B and the fiber-impregnated resin described later.
As the binder resin, one type may be used alone, or two or more types may be used in combination.

Examples of the binder resin include polyurethane resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, acrylic resin / acrylonitrile resin / acrylamide resin copolymer, and chlorinated polypropylene resin. , Acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin, silicone resin and the like.
Since the molding temperature preferably reaches about 150 ° C. in integral molding, the binder resin is preferably a resin designed to have a glass transition temperature of less than 150 ° C., and an acrylic resin having a glass transition temperature of less than 150 ° C. It is more preferable to contain at least one resin selected from the group consisting of the polyester resin and the polyester resin.

In the present specification, the glass transition temperature of the binder resin means a value measured by differential scanning calorimetry (DSC), and can be obtained by, for example, the following measuring method.
The dispersion of the binder resin is taken out into a petri dish and dried in an oven to prepare a dry solid film of the binder resin. 10 mg was sampled from the obtained dry solid film, and the temperature was raised to 160 ° C. at a heating rate of 20 ° C./min using differential scanning calorimetry (DSC) (product name manufactured by TA Instruments Co., Ltd .; Q100) and held for 5 minutes. After that, it was rapidly cooled to return the sample temperature to room temperature, and then when the measurement was performed again at a temperature rise rate of 20 ° C./min, the midpoint where the shift to the endothermic side of the baseline was observed was set as the glass transition temperature. calculate.

The easy-adhesive layer A is preferably a layer formed by applying a coating liquid for forming an easy-adhesive layer containing the above binder resin and a specific cross-linking agent onto the base film B, and is preferably a film-forming layer of the base film B. In the step, it is more preferable that the layer is formed by applying a coating liquid for forming an easy-adhesive layer to the base film B (hereinafter, may be referred to as “in-line coating”). In particular, the easy-adhesive layer A which has been coated on the base film B and then stretched once or more as a laminate with the base film B is preferable.
As a method for producing the surface coating film, the easy-adhesion layer A is formed by coating during or during any of the steps until all the stretching to be made into the unstretched base film B is completed. It is preferable to do so.

The specific cross-linking agent contained in the coating liquid for forming an easy-adhesive layer is preferably used by being dispersed in a solvent or water.
When the specific cross-linking agent is dispersed in a solvent, examples of the solvent include solvents such as methyl ethyl ketone, butyl acetate, and toluene, which are generally used as solvents.
Further, when the coating liquid for forming the easy-adhesive layer is applied during the film-forming of the base film B to form the easy-adhesive layer A, it is specified because the film-forming device of the base film B is an open system. It is particularly preferable to use the cross-linking agent dispersed in water.

The coating liquid for forming an easy-adhesion layer may contain a component known as a coating liquid such as a surfactant, and is a filler for slipperiness, an ultraviolet inhibitor, and an antioxidant to the extent that the effect of the present invention can be obtained. Additives such as may be added.

Examples of the filler include inorganic fillers such as metal hydroxides, metal oxides, carbonates, sulfates and clay minerals; organic fillers such as particles made of crosslinked polymers and particles made of heat-resistant polymers.
When the coating liquid for forming an easy-adhesion layer contains a filler, the filler is preferably an inorganic filler, more preferably alumina, silica or mica.

The average particle size of the filler is preferably 0.02 μm to 0.2 μm, more preferably 0.04 μm to 0.1 μm.

When the coating liquid for forming an easy-adhesion layer contains a filler, the content of the filler is preferably 1% by mass to 10% by mass, more preferably, with respect to the total mass of the coating liquid for forming an easy-adhesion layer. It is 3% by mass to 5% by mass.

The coating liquid for forming an easy-adhesion layer may contain a colorant used in a decorative layer described later.
The colorant has the same meaning as the colorant used in the decorative layer described later, and the preferred embodiment is also the same.

When the coating liquid for forming an easy-adhesion layer contains a colorant, the colorant content is preferably 1% by mass to 10% by mass, more preferably, with respect to the total mass of the coating liquid for forming an easy-adhesion layer. It is 3% by mass to 5% by mass.

The coating of the coating liquid for forming the easy-adhesion layer is not particularly limited, and coating is performed using known coating equipment and coating methods such as roll coaters, gravure coaters, microgravure coaters, bar coaters, die coaters, and dip coaters. Can be worked on. Among these, as the coating method, it is preferable to use a roll coater by the reverse method for the purpose of uniformly and easily forming a desired thickness.

Examples of the method for drying or curing the coating liquid for forming an easy-adhesive layer include a method of heat-treating at 180 ° C. to 220 ° C. In the easy-adhesive layer A, the coating liquid for forming an easy-adhesive layer is dried and cured by heat treatment. The layer is preferably formed by heat treatment at 180 ° C. to 220 ° C., and more preferably the layer is formed by heat treatment.
When the coating liquid for forming an easy-adhesive layer is applied by the above-mentioned in-line coating, if the heat treatment temperature at the time of biaxial stretching is within the above range, curing is performed while appropriately leaving unreacted specific functional groups in the specific cross-linking agent. Since this can be performed, the adhesion between the fiber-impregnated resin and the easy-adhesion layer A can be improved in the integral molding process, the heat shrinkage of the base film B can be reduced, and the appearance defect at the time of integral molding can be controlled. can.
From the above viewpoint, the heat treatment temperature is preferably 180 ° C. to 220 ° C., more preferably 190 ° C. to 215 ° C., and even more preferably 195 ° C. to 210 ° C.
Prior to the in-line coating, a surface treatment such as a corona treatment, a frame treatment, or a plasma treatment may be applied to the base film B, if necessary.
The heat treatment time can be appropriately set, and is preferably 1 second to 60 seconds, more preferably 1 second to 30 seconds.
Further, the heat treatment may be performed by relaxing the base film B in the longitudinal direction and / or the width direction.

The refractive index of the easy-adhesion layer A at a wavelength of 633 nm is preferably 1.50 to 1.58, more preferably 1.51 to 1.56, from the viewpoint of vividness.
For the refractive index of the easy-adhesion layer A, the prepared water-dispersed paint was dried in an oven at 80 ° C. for one day to remove water, and then the refractive index of the obtained resin dry solid film was measured by a laser refractive index measuring device ( It can be obtained by measuring at a wavelength of 633 nm using a product name; MetriconModel 2010 prism coupler, manufactured by Metricon.

<< Other layers >>
The surface coating film may further have a layer other than the easy-molding layer b1, the flat layer b2, and the easy-adhesive layer A (hereinafter, also referred to as “functional layer”). When the surface coating film has a functional layer, the function is preferably formed on the side opposite to the easy-adhesive layer A in the surface coating film, and the flat layer b2 on the opposite side of the easy-contact layer A in the surface coating film. It is more preferable that it is formed on the surface.
Examples of the functional layer include a decorative layer, a clear pearl layer, a hard coat layer and the like.

<< Decorative layer >>
The components constituting the decorative layer are not particularly limited, and examples thereof include a binder resin, a pigment, a dye, and if necessary, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like. A decorative layer can be formed by appropriately mixing.
The colorant is not particularly limited, and white pigments such as carbon black (black), iron black, titanium white (titanium dioxide) and antimony white, yellow lead, titanium yellow, petal pattern, cadmium red, ultramarine, and cobalt blue. From inorganic pigments such as quinacridone red, isoidrinone yellow, organic pigments or dyes such as phthalocyanine blue, metal pigments consisting of scaly foil pieces such as brass, titanium dioxide coated mica, and scaly foil pieces such as basic lead carbonate. Examples include pearl luster (pearl) pigments.
The binder resin used for mixing the colorants preferably has moldability.

<Manufacturing method of base film B and surface coating film>
As an embodiment of the method for producing the base film B and the surface coating according to the present invention, an example in which the biaxially stretched polyester film is used as the base film B will be described below.

As described above, the base film B is preferably biaxially stretched, that is, a biaxially oriented film. By axially stretching the base film B, it is expected that the chemical resistance and durability will be improved, and the strength as a film can be imparted.
As the base resin (polyester resin in the example here) which is the main component of each layer constituting the base film B, the easily molded layer b1 and the flat layer b2 satisfy the above-mentioned formulas 1 and 2 regarding the storage elastic modulus. There is no particular limitation as much as possible, and for example, a commercially available resin raw material may be purchased and polycondensed by a known method.
As a means for making the easily molded layer b1 and the flat layer b2 satisfy the above-mentioned formulas 1 and 2 regarding the storage elastic modulus, information on the storage elastic modulus of the resin is obtained from academic literature and a database on the physical characteristics of the resin. The composition / composition of each layer may be determined with reference to the information. Of course, the composition of each layer is based on the information obtained by actually measuring the storage elastic modulus of the film produced by obtaining each resin and the laminated body thereof, and simulating the physical properties of the film by a computer. The ingredients may be determined. In addition, based on the above information, the physical properties of the surface coating film obtained by trial production are measured, and if there are any unfavorable points, the materials and conditions are adjusted (resin copolymer composition, additives, and layer thickness). It is also possible to obtain a surface coating film in which the easy-to-mold layer b1 and the flat layer b2 satisfy the formulas 1 and 2 by repeating (changing, etc.) several times.

-Preparation process-
The preparation step includes a step of drying the resin as a raw material.
The drying method is not particularly limited, but it is preferable to perform drying at 160 ° C. for about 5 hours in a nitrogen atmosphere, a vacuum atmosphere, or the like. The drying temperature and drying time are not particularly limited as long as the water content in the polyester resin is preferably 50 ppm or less.
When melt extrusion is performed using a vent type twin-screw extruder, the preparation step for drying the resin as a raw material may be omitted.

-Melting extrusion process and film forming process-
In the melt extrusion step, the polyester resin raw material obtained in the above preparation step is put into an extruder and melt-kneaded in a cylinder.
In the method for producing the base film B, the molten polyester resin is removed from foreign substances and the extrusion amount is proportionalized through a filter or a gear pump, and is discharged from a T-die onto a cooling drum in the form of a sheet to form a film. It is preferable to include a step (film forming step).
At this time, it may be extruded in a single layer or in multiple layers. The melt-extruded molten polyester resin is preferably cooled on a support, solidified, and formed into a sheet.

In the film forming step, the polyester resin melt-extruded in the melt extrusion step can be cooled to form a polyester resin sheet (base film B). In the film forming process, for example, a method of electrostatically applying using a wire-shaped electrode or a tape-shaped electrode, a casting method of providing a water film between a casting drum and an extruded polymer sheet, and a casting drum temperature of polyester glass transition point to The sheet-like polymer is brought into close contact with the casting drum, cooled and solidified, and unstretched polyester resin film by a method of adhering the extruded polymer by adjusting the glass transition point to -20 ° C or a method of combining a plurality of these methods. (Base film) may be obtained.
Among these casting methods, the method of electrostatically applying is preferable from the viewpoint of productivity and flatness of the polyester resin.

-Forming process of easy-adhesion layer A-
It is preferable that the step of forming the easy-adhesion layer A is performed during or during any of the steps until all the stretching to be made into the unstretched base film B is completed.
As a step of forming the easy-adhesive layer A, the above-mentioned coating liquid for forming an easy-adhesive layer is applied to the base film B at a temperature suitable for coating at the final stage or after the film forming process of the base film B ( The step of forming the easy-adhesion layer A by in-line coating) is exemplified.
The coating method, heat treatment conditions, etc. of the coating liquid for forming the easy-adhesive layer are as described above, and may be applicable to the formation of other layers of the surface coating film.

-Stretching process-
In the stretching step, as a method of stretching the unstretched polyester film obtained in the melt extrusion step, the unstretched polyester film is stretched in the longitudinal direction and then stretched in the width direction, or after stretching in the width direction. Examples thereof include a sequential biaxial stretching method in which the unstretched polyester film is stretched in the longitudinal direction, and a simultaneous biaxial stretching method in which the unstretched polyester film is stretched substantially simultaneously in the longitudinal direction and the width direction, and can be appropriately selected.

The draw ratio varies depending on the type of resin, but is preferably 2.5 times to 4.0 times, more preferably 2.8 times to 3.5 times, and 3.0 times to 3.4 times in the width direction. And it is more preferably stretched in the longitudinal direction.

From the viewpoint of film formation stability, the area magnification is preferably 6 to 20 times, and in the case of a film using polyethylene terephthalate (PET), the area magnification is more preferably 8 to 20 times.

Further, the stretching speed is preferably 1,000% / min to 200,000% / min in the stretching directions in the width direction and the longitudinal direction.

The stretching temperature is preferably a glass transition temperature or higher to a glass transition temperature of 120 ° C. or lower, and a glass transition temperature of + 10 ° C to a glass transition temperature of + 60 ° C. In particular, it is preferable that the stretching temperature in the longitudinal direction is 80 ° C. to 120 ° C. and the stretching temperature in the width direction is 90 ° C. to 110 ° C.
The stretching may be performed a plurality of times in each direction.
As the stretching method, a known and publicly available method can be applied, and any of the stretching methods such as roll stretching or a stretching method of guiding the film to a tenter and transporting the film while gripping both ends with clips can be adopted.

-Heat treatment process-
In order to impart flatness and dimensional stability to the biaxially stretched surface coating film, it is preferable to further perform heat treatment in the tenter at the stretching temperature or higher and the melting point or lower.
In order to suppress the orientation distribution in the width direction, it is preferable to perform the relaxation treatment in the longitudinal direction instantly immediately before and / or immediately after entering the heat treatment zone.

The biaxially stretched surface coating film is heat-treated, slowly cooled uniformly, cooled to room temperature, and then wound up.
Further, if necessary, a relaxation treatment may be performed in the longitudinal direction and / or the width direction during the heat treatment to the slow cooling.

The surface coating film according to the present invention obtained by the above manufacturing method preferably has an elongation at 150 ° C. of 100% or more in the film forming direction and the width direction. The upper limit of the elongation at 150 ° C. is not particularly limited, and the higher it is, the more preferable.
When the elongation at 150 ° C. of the surface coating film is 100% or more with respect to the film forming direction and the width direction, the shape of the fiber reinforced resin described later can be followed.

When the surface coating film is stretched, the tensile stress increases. The tensile stress of the surface coating film is preferably low because it becomes a resistance to the molding force at the time of integral molding with the fiber reinforced resin. On the other hand, if it is too low, the convex portion of the base material shape is excessively stretched, and problems such as thickness unevenness are likely to occur.
From the viewpoint of smoothness, the tensile stress of the surface coating film at 150 ° C. is preferably 3 MPa to 50 MPa, more preferably 5 MPa to 30 MPa.
It is preferable that the tensile stress of the surface coating film tends to increase monotonically with elongation. "It increases monotonically with elongation" means that when the elongation is on the horizontal axis and the stress is on the vertical axis, the increase in tensile stress becomes 0 or negative, that is, the slope becomes zero or less at the stage until fracture. It means that the region has an elongation to break of 30% or less, and further 20% or less.

As a result obtained by the above-mentioned manufacturing method, the surface coating film according to the present invention has an absolute value Δχ of the heat shrinkage difference when the heat shrinkage in the film forming direction at 150 ° C. is χMD and the heat shrinkage in the width direction is χTD. It is preferable to satisfy the following formula (1).
Δχ = | χMD-χTD | ≤3.0 ... (1)
When Δχ is 3.0 or less, the difference in heat shrinkage of the base film B is small, and the appearance after integral molding can be kept good. If the lower limit of Δχ is intentionally set, it is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more in that it is easy to achieve even in industrial scale production. , 1.0 or more is more preferable, and 1.5 or more is particularly preferable.

The surface coating film according to the present invention preferably has a total light transmittance of 80% or more with respect to visible light.
When the total light transmittance is 80% or more, the texture can be expressed as a design when the fiber reinforced resin contains carbon fiber, for example, and when a decorative layer or the like is provided, the design of the decorative layer can be expressed. Can be expressed more effectively. The total light transmittance is more preferably 82% or more, still more preferably 85% or more.

(Surface coated fiber reinforced resin molded product)
The surface-coated fiber-reinforced resin molded product (hereinafter, also referred to as “fiber-reinforced resin molded product”) according to the present invention is a molded product in which the above-mentioned surface-coated film and the fiber-impregnated resin are integrally molded.
-Fiber impregnated resin-
The fiber impregnated resin is composed of a fiber and a resin (hereinafter, also referred to as "matrix resin"), and is a resin in which a part or all of the inside of the fiber is impregnated with the matrix resin and the fiber and the matrix resin are integrated. be.
The matrix resin contained in the fiber-impregnated resin may be a thermosetting resin or a thermoplastic resin, but a thermosetting resin is preferable.
When the matrix resin is a thermoplastic resin, the thermoplastic resin is not particularly limited, and a polyolefin (for example, polyethylene, polypropylene, polybutylene and polystyrene), a polyamide (for example, nylon 6, nylon 66, nylon 11, nylon 12, nylon 12, etc.), polyamide (for example, nylon 6, nylon 66, nylon 11, nylon 12, etc.), Nylon 610 and semi-aromatic nylon), polyimide, polyamideimide, polycarbonate, polyester (eg polyethylene terephthalate, polybutylene terephthalate and polypropylene terephthalate), polyphenylene sulfide, polysulfoxide, polytetrafluoroethylene, acronitrile butadiene styrene co-weight Examples thereof include coalescence, polyacetal, polyether, polyether ether ketone, polyoxymethylene, and thermoplastic epoxy resin. Further, it may be a derivative of the above-mentioned thermoplastic resin, a copolymer of the above-mentioned thermoplastic resin, or a mixture thereof.

When the matrix resin is a thermoplastic resin, the molding temperature (Ts) when the surface coating film and the fiber-impregnated resin are integrally molded may be lower than the softening point (Tn) of the resin contained in the base film B. It is more preferable to satisfy the relationship of Tn ≦ Ts −10 ° C., and further preferably satisfy the relationship of Tn ≦ Ts −20 ° C.

When the matrix resin is a thermosetting resin, the thermosetting resin is not particularly limited, and the thermosetting epoxy resin, unsaturated polyester resin, vinyl ester resin, phenol resin, melamine resin, polyurethane resin, silicone resin, etc. Examples thereof include a maleimide resin, a cyanate ester resin, and a resin obtained by prepolymerizing a maleimide resin and a cyanate ester resin. Further, it may be a mixture of these resins.
When a fiber-reinforced composite material is used, an epoxy resin is preferable as the thermosetting resin from the viewpoint of excellent heat resistance, elastic modulus and chemical resistance.

When the matrix resin is a thermosetting resin, the curing rate of the thermosetting resin is preferably 10 minutes or less at 150 ° C. Further, from the viewpoint of shortening the curing time and improving the moldability, the thermosetting resin is preferably an epoxy resin having a curing speed of 150 ° C. and a curing time of 10 minutes or less.

When the matrix resin is a thermosetting resin, the glass transition temperature of the thermosetting resin is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher. .. When the glass transition temperature of the thermosetting resin is 80 ° C. or higher, the cured product of the thermosetting resin becomes a rubber state even when the ambient temperature becomes 80 ° C. or higher during the use of the surface-coated laminate. Since it is difficult to become, the smoothness of the surface of the surface coating film is easily maintained.
The glass transition temperature of the thermosetting resin can be obtained, for example, by the same method as the glass transition temperature of the binder resin described above.

The content of the matrix resin (RC) is preferably 20% by mass to 60% by mass, more preferably 20% by mass to 50% by mass, and 25% by mass, based on the total mass of the fiber-impregnated resin. It is more preferably to 45% by mass.
When the content of the matrix resin is 20% by mass or more, voids and the like are less likely to occur in the obtained molded product, and mechanical properties and the like are likely to be imparted. When the content of the resin is 60% by mass or less, the reinforcing effect of the fibers can be obtained, and mechanical properties and the like can be imparted.

Here, the content rate (RC) of the matrix resin is determined by immersing the fiber-impregnated resin in sulfuric acid to elute the matrix resin impregnated in the fiber-impregnated resin. Specifically, it is obtained by the following method.
First, the fiber-impregnated resin is cut into 100 mm × 100 mm to prepare a test piece, and the mass thereof is measured. Next, the test piece of the fiber-impregnated resin is immersed in sulfuric acid and boiled if necessary. As a result, the resin impregnated in the fiber-impregnated resin is decomposed and eluted in sulfuric acid. Then, the remaining fibers are filtered off, washed with water, dried, and the mass of the fibers is measured. The content of the matrix resin can be calculated from the mass change before and after the decomposition operation with sulfuric acid.

The fiber contained in the fiber impregnated resin is not particularly limited, and examples thereof include glass fiber, carbon fiber, aramid fiber, boron fiber, alumina fiber, basalt fiber, and silicon carbide fiber. These fibers may be one kind or a combination of two or more kinds. The fiber-impregnated resin preferably contains carbon fibers from the viewpoint of obtaining a molded product having a lighter weight and higher durability.

The shape of the fibers contained in the fiber-impregnated resin is preferably a sheet-like fiber (fiber reinforced sheet). The fiber reinforced sheet is not particularly limited, but for example, a sheet in which a large number of fibers are arranged in one direction, a bidirectional woven fabric such as plain weave or twill weave, a multi-axis woven fabric, a non-woven fabric, a mat, a knit, a braid, or a reinforced sheet. Examples include paper made from fibers.

The content of the fiber contained in the fiber-impregnated resin is preferably 40% by mass to 80% by mass with respect to the total mass of the fiber-impregnated resin. When the fiber content is 40% by mass or more with respect to the mass of the fiber-impregnated resin, the mechanical properties of the obtained surface-coated laminate can be improved. When the content of the fiber is 80% by mass or less, the decrease in fluidity during molding can be suppressed, and the fiber can be sufficiently impregnated with the resin component of the fiber-impregnated resin, resulting in dynamics. The characteristics can be improved.
Further, when the fiber content is in the above range, the smoothness of the surface coating film and the surface coating laminate can be improved, and the appearance of the laminated sheet can be further improved.

When the fiber reinforced sheet is a multi-axis woven fabric, examples of the preferred multi-axis woven fabric are [+ 45 / -45], [-45 / + 45], [0/90], [0 / + 45 / -45], [ 0 / -45 / + 45], [0 / + 45/90 / -45] and the like.
The above 0, ± 45 and 90 represent the stacking angle of each layer constituting the multi-axis woven fabric, and the fiber axis direction of the reinforcing fibers aligned in one direction is 0 °, ± with respect to the length direction of the woven fabric, respectively. It shows that it is 45 ° and 90 °. The stacking angle is not limited to these angles and can be any angle.
The basis weight of the multi-axis woven fabric is preferably 200 g / m ² to 1000 g / m ² per sheet, and more preferably 200 g / m ² to 800 g / m ² .

When the fiber reinforced sheet is a two-way woven fabric, examples of the two-way woven fabric include known woven fabrics such as plain weave, satin weave, and twill weave.
The basis weight of the two-way woven fabric is preferably 60 g / m ² to 400 g / m ² per sheet, and more preferably 60 g / m ² to 250 g / m ² .
When the fiber reinforced sheet is matte or paper-made paper, the number average fiber length of the fibers is preferably 0.1 mm to 100 mm. More preferably, it is 0.5 mm to 50 mm.
By setting the number average fiber length of the fibers to 0.1 mm or more, the reinforcing effect of the fibers can be improved. On the other hand, by setting the number average fiber length of the reinforcing fibers to 100 mm or less, the springback of the surface coating film can be suppressed, the smoothness of the surface coating film can be further improved, and the cracks inside the surface coating film can be further improved. It is possible to suppress the occurrence of (cracks) and cavities.

As a method of measuring the number average fiber length of the fibers contained in the fiber impregnated resin, heat treatment is performed in a temperature range in which the fibers are not oxidatively reduced, and only the resin component (matrix resin) of the fiber impregnated resin is burned off to obtain the resin component and the fiber. After sorting, 400 fibers were randomly selected by observing with an optical microscope, the length of the selected fibers was measured to the unit of 1 μm, and the number average value of these was calculated to calculate the number average fiber length. It can be confirmed by the method (burning method). The burn-off method can also be applied when there is no solvent to dissolve the matrix resin.

(Manufacturing method of surface-coated fiber reinforced resin molded product)
A surface-coated fiber-reinforced resin molded product (fiber-reinforced resin molded product) can be manufactured by contacting and integrally molding the easy-adhesion layer A in the surface-coated film according to the present invention and the fiber-impregnated resin.
One embodiment of the method for manufacturing a fiber-reinforced resin molded product according to the present invention includes a step (integral molding step) of contacting and integrally molding the easy-adhesion layer A in the surface coating film and the fiber-impregnated resin.
Hereinafter, preferred embodiments of each step of the fiber-reinforced resin molded product according to the present invention and the fiber-reinforced resin molded product according to the present invention will be described in order.
In the method for producing a fiber-reinforced resin molded product, the above-mentioned method for producing a surface coating film may be further included as a step.
It should be noted that each step of the method for producing the surface coating film is as described above, and a preferred embodiment of each step of the method for producing the surface coating film in the method for producing the fiber-reinforced resin molded product is each of the methods for producing the surface coating film. It is synonymous with process.

<Integral molding process>
The step included in the method for producing a fiber-reinforced resin molded product according to the present invention is a step of integrally molding the fiber-impregnated resin and the surface coating film according to the present invention, preferably fiber-impregnated by heat-press molding. This is a process of integrally molding the resin and the surface coating film.
In the integral molding by heat and pressure molding, when a thermosetting resin such as an epoxy resin is used as the matrix resin of the fiber impregnated resin, the matrix resin can be cured at the same time as the integral molding. Further, when a thermoplastic resin is used as the matrix resin of the fiber impregnated resin, the matrix resin can be integrally molded while being softened, so that the production efficiency is excellent.

The heat-press molding method is not particularly limited, and a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method, an internal pressure molding method, etc. can be adopted. From the viewpoint of enhancing, the press molding method is preferable.
The molding temperature (or curing time) in the heat-pressing molding method may be appropriately selected depending on the selected matrix resin. For example, when an epoxy resin composition is used as the matrix resin, the type of curing agent contained in the composition and the like may be used. However, from the viewpoint of quick curing, a temperature of 80 ° C. to 180 ° C. is usually preferable.

The pressure for molding by the press molding method varies depending on the thickness of the fiber-impregnated resin and the like, but is usually preferably 0.1 MPa to 5 MPa. Since heat can be sufficiently transferred to the inside of the fiber-impregnated resin, which is 0.1 MPa to 5 MPa, and the resin contained in the fiber-impregnated resin can be sufficiently cured, the occurrence of warpage is reduced and the surface appearance is improved. Is also excellent.

The integral molding step is preferably a step of integrally molding the fiber-impregnated resin at 150 ° C. for 10 minutes or less.
When the curing conditions are 150 ° C. and 10 minutes or less, the time until the curing is completed can be shortened, and the moldability can be further improved.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In addition, each value in this Example was obtained according to the following method.

<Preparation of coating liquid for forming an easy-adhesion layer>
The coating liquid for forming the easy-adhesive layer was prepared by mixing the specific cross-linking agent and the binder resin in the ratios shown in Table 1. The coating liquid for forming the easy-adhesion layer was prepared by adding an additive paint such as a main binder resin dispersion paint and a curing agent dispersion paint to ion-exchanged water and stirring and dispersing the coating liquid to obtain a water-dispersed paint. If necessary, a surfactant was further added to prepare the total in the solid content to be 100%, and the coating liquid for forming an easy-adhesion layer was stirred and dispersed so as to have a solid content concentration of 3%.
Further, a coating liquid for forming an easy-adhesion layer was supplied by a pump, passed through a filter to remove foreign substances, and then stored in a coating liquid pan, which was used when producing a surface coating film.

The binder resin contained in the coating liquid for forming the easy-adhesion layer is as follows.
<< Acrylic A >>
An acrylic resin copolymer obtained by subjecting 40 mol% of methyl methacrylate, 45 mol% of ethyl acrylate, 10 mol% of acrylonitrile and 5 mol% of N-methylolacrylamide to an addition condensation reaction.
The weight average molecular weight is 220,000. The weight average molecular weight was measured by the method described above. Hereinafter, the weight average molecular weight was measured in the same manner.

<< Acrylic B >>
An acrylic resin copolymer obtained by subjecting 75 mol% of methyl methacrylate, 20 mol% of ethyl acrylate, and 5 mol% of N-methylolacrylamide to an addition condensation reaction.
The weight average molecular weight is 200,000. The weight average molecular weight was measured by the method described above. Hereinafter, the weight average molecular weight was measured in the same manner.

<< Polyester >>
A polyester resin obtained by blending a polyester resin 1 and a polyester resin 2 composed of the following copolymerization components so as to have a mass ratio of 1: 1. The weight average molecular weight is 21,000.
Polyester resin 1; A polyester resin obtained by synthesizing 40 mol% of terephthalic acid as a carboxylic acid component and 60 mol% of ethylene glycol as a glycol component. The weight average molecular weight is 20,000.
Polyester resin 2; A polyester resin obtained by synthesizing 65 mol% of naphthalenedicarboxylic acid and 35 mol% of isophthalic acid as a carboxylic acid component and 60 mol% of ethylene glycol as a glycol component. The weight average molecular weight is 13,000.

<< Polyester-Acrylic Blend >>
A resin composition obtained by blending the following polyester resin 3 and the above acrylic A in a mass ratio of 1: 1.
Polyester resin 3; A resin obtained by synthesizing terephthalic acid as a carboxylic acid component and a glycol component of ethylene glycol and diethylene glycol at a molar ratio of 90:10.
The weight average molecular weight is 19,000.

[Example 1]
<Preparation of surface coating film>
Polyester P1 was obtained by polymerizing terephthalic acid and ethylene glycol.
Further, a carboxylic acid component of terephthalic acid and isophthalic acid (terephthalic acid: isophthalic acid = 90:10 [molar ratio]) and ethylene glycol were polymerized to obtain polyester P2. Further, polymerization was carried out using terephthalic acid as a carboxylic acid component and butylene glycol as a glycol component to obtain polyester Q.
Further, a treatment in which aggregated silica particles (manufactured by Fuji Silysia Chemical Ltd.) having an average particle size of 1.7 μm were contained in polyester P2 in the order of ppm was carried out by a known method to obtain polyester R.

The polyesters P2, Q and R prepared above are dried at 160 ° C. for 4 hours to remove water, and then supplied to the hopper so that the weight ratio is polyester P2 / polyester Q / polyester R = 50/45/5. After mixing the chips, the melt was extruded into a sheet from an extruder set at 280 ° C. using a die.
When performing melt extrusion into a sheet, polyester P1 is merged from the die using a feed block, and a layer containing polyester P1 (flat layer b2) is placed on a layer containing polyester P2, Q and R (easy forming layer b1). ) Is laminated so that the thickness ratio of the easy-molding layer b1 and the flat layer b2 is 3: 7, extruded as two layers, and immediately cooled by a casting drum at 20 ° C. to cast a film (base material). Film B) was obtained.

In the subsequent longitudinal stretching step, the obtained cast film was stretched 3.0 times at 90 ° C. to obtain a uniaxial film. The coating liquid for forming the easy-adhesive layer prepared above is applied to the surface of the layer (easy-molding layer b1) containing polyester P2 in the above-mentioned uniaxial film by a roll coater so that the film thickness of the easy-adhesive layer A becomes the thickness shown in Table 1. Then, the film was led to a stainless steel step to dry the coating film to form the easy-adhesion layer A.
The obtained uniaxial film was stretched so that the lateral stretching was 3.2 times at 105 ° C., and while being treated at 210 ° C. in the crystallization zone, it was relaxed in the 1% width direction to cause thermal shrinkage. With this restraint, a surface coating film, which is a biaxially stretched film having a thickness of 50 μm, was formed and wound into a roll.
The heat shrinkage of the surface coating film at 150 ° C., the storage elastic modulus of the easy-molding layer b1 and the flat layer b2 at each temperature, the thickness of the easy-adhesion layer A, and the presence or absence of the epoxy group and the oxazoline group in the easy-adhesion layer A are determined by the methods described below. The measurements were made and the results are shown in Table 1.

<< Heat shrinkage of surface coating film at 150 ° C >>
The heat shrinkage at 150 ° C. in the film forming direction (MD direction) and the width direction (TD direction) of the surface coating film in Table 1 was measured by the following method.
The base film B was cut into a size of 40 cm × 40 cm and used as an evaluation sample. After marking points at intervals of 30 cm in the film forming direction (MD direction) and the width direction (TD direction) of this evaluation sample, heat treatment was performed in an oven at 150 ° C. for 30 minutes. After the heat treatment, the evaluation sample is cooled to room temperature, the length between the gauge points before the heat treatment is subtracted from the length between the gauge points after the heat treatment, and the heat shrinkage ratio is divided by the dimensions before the heat treatment. %).

<< Thickness of Easy Contact Layer A >>
The thickness of the easy-contact layer A in Table 1 was measured by the following method.
The surface coating film was sampled with a small test piece, embedded in an epoxy resin, cured, and then ultrathin sections were prepared using a microtome, and the cross section thereof was observed with a TEM (transmission electron microscope). From the obtained image and scale, the thickness of the easy contact layer A was calculated. Measurement / analysis samples can be collected from other layers of the surface coating film according to the above procedure.

<< Content of Epoxy Group and Oxazoline Group in Easy Contact Layer A >>
The content of the functional group was confirmed using 1 H-NMR with respect to the ultrathin section obtained by the manufacturing method for measuring the thickness of the easy-contact layer A.

<< Storage modulus ELb1 >>
The storage elastic modulus ELb1 of the easy-molding layer b1 at 23 ° C. is obtained by pulling the easy-molding layer b1 in the MD direction with a tension jig using a dynamic viscoelasticity measuring device (product name; DMA8000, manufactured by PerkinElmer Co., Ltd.) at 1 Hz. The storage elastic modulus at 23 ° C. under the frequency of was measured.

<< Storage modulus EHb1 >>
In the measurement of the storage elastic modulus ELb1, the storage elastic modulus of the easily molded layer b1 at 150 ° C. was measured in the same manner as the measurement of the storage elastic modulus ELb1 except that the measurement temperature was set to 150 ° C.

<< Storage modulus EHb2 >>
In the measurement of the storage elastic modulus ELb1, the storage elastic modulus of the flat layer b2 at 150 ° C. was measured in the same manner as the measurement of the storage elastic modulus EHb1 except that the flat layer b2 was used instead of the easy-molding layer b1. ..

<Manufacturing of fiber reinforced resin molded products>
Five fiber-impregnated resins (carbon fiber reinforced prepreg made of epoxy resin, Tenax (registered trademark) W-3101 / Q-195, manufactured by Teijin Limited) were laminated to prepare a laminated fiber-impregnated resin. After laminating the easy-adhesion layer A of the surface coating film obtained above so as to be in contact with the laminated body of the fiber-impregnated resin, integral molding was performed by press molding at a molding temperature of 150 ° C., and the curing time was 5 minutes. An integrally molded product of carbon fiber reinforced resin was obtained.
The following evaluation was performed using the obtained integrally molded product of carbon fiber reinforced resin (hereinafter, also simply referred to as “integrally molded product”). The results are shown in Table 1.

<Evaluation of surface coating film>
(1) Adhesion The surface of the surface coating film of the integrally molded product obtained above was cut to a depth reaching the base film B to provide a grid-like scratch for 100 squares. A polyester adhesive tape (product name; No. 31B, manufactured by Nitto Denko KK) was attached so as to cover the entire grid-like scratches, and the adhesive tape was peeled off. The surface of the surface coating film after peeling was observed with an optical microscope (35 times), the number of peeling and coating film cracking was measured, and the adhesion with the fiber-reinforced resin was evaluated according to the following criteria. The results are shown in Table 1.
-Evaluation criteria-
A: No peeling or cracking of the coating film is observed, and the adhesion is excellent.
B: The number of peeling or coating film cracking is one, and the adhesion is slightly excellent.
C: The number of peeling or coating film cracking is 2 to 10, and the adhesion is slightly inferior.
D: The number of peeling or coating film cracking is 11 or more, and the adhesion is inferior.

(2) Vividness The obtained integrally molded product was visually observed under a fluorescent lamp (Panasonic Corporation 3-wavelength neutral white FHF24SEN 24W). When the reflection of the fluorescent lamp was visually confirmed, the distortion of the fluorescent lamp image projected on the surface of the surface coating film of the integrally molded product was observed, and the vividness was evaluated based on the following evaluation criteria. The distortion of the fluorescent lamp image is specular, and the observation angle is the angle from the horizontal plane.
-Evaluation criteria-
A +: When the observer observes the fluorescent lamp image projected on the surface of the surface coating film of the integrally molded product, the distortion of the fluorescent lamp image is not observed regardless of the observation angle, and the integrally molded product is glossy and good. A-: When the observer observes the fluorescent lamp image projected on the surface of the surface coating film of the integrally molded product at an observation angle of 45 degrees or more, the distortion of the fluorescent lamp image is not observed. When observed at less than 45 degrees, distortion of the fluorescent lamp image is observed, the integrally molded product is glossy, and a good reflection image is obtained.
B: When the observer observes the fluorescent lamp image projected on the surface of the surface coating film of the integrally molded product at an observation angle of 45 degrees, the fluorescent lamp image is partially distorted, and the integrally molded product is glossy and relatively. Good reflection image is obtained C: When the observer observes the fluorescent lamp image projected on the surface of the surface coating film of the integrally molded product at an observation angle of 45 degrees, the fluorescent lamp image is totally distorted and integrated. The molded product is glossy, but the reflected image is not clear. D: When the observer observes the fluorescent lamp image projected on the surface of the surface coating film of the integrally molded product at an observation angle of 45 degrees, the fluorescent lamp image is displayed. Overall distortion, poor gloss of integrally molded product, not clear reflected image

(3) Glossiness Using a handy gloss meter (product name; PG-IIM, manufactured by Nippon Denshoku Kogyo Co., Ltd.), the 60 ° gloss value (glossiness) of the surface coating film surface of the integrally molded product was measured. The larger the measured value, the better the glossiness.
(4) Total light transmittance Total light transmittance Total light transmittance (unit:%) of the surface coating film is measured using a haze measuring instrument (NDH-2000) manufactured by Nippon Denshoku Kogyo Co., Ltd. according to JIS K7361. Then, the average light transmittance at 300 to 800 nm was read.

[Examples 2 to 8 and Comparative Examples 1 to 6]
In Example 1, a surface coating film was produced in the same manner as in Example 1 except that the composition and thickness were changed to those shown in Table 1 or Table 2, and an integrally molded carbon fiber reinforced resin was obtained by press molding. Each of the obtained integrally molded products was evaluated in the same manner as in Example 1. In all the examples except Example 6, the total light transmittance of the surface coating film was 80% or more.

MD in Tables 1 and 2 means the longitudinal direction, and TD means the width direction. The abbreviations in Tables 1 and 2 are as follows.
-PET; polyester resin, weight average molecular weight; 20,000 (polyester P1)
-IAPET // PBT; copolymer of polyethylene isophthalate and polybutylene terephthalate, weight average molecular weight; 75,000 (polyester P2)
PEN; polyethylene-2,6-naphthalate, weight average molecular weight; 10,000
-PUE; polyurethane resin, weight average molecular weight; 40,000

The compounds used to prepare the surface coating films of Tables 1 and 2 are shown below.

(Filler with easy adhesive layer A added)
-Silica; manufactured by Nissan Chemical Industries, Ltd., trade name; "ST-OL"

(Fiber impregnated resin)
W-3101 / Q-195; carbon fiber reinforced prepreg made of epoxy resin, product name; woven fabric prepreg "Tenax" (registered trademark) W-3101 / Q-195, manufactured by Toho Tenax Co., Ltd. Fiber grain: 197 g / m ^2. Resin content: 40% by mass, curing time at 150 ° C. for 5 minutes.

The specific cross-linking agent contained in the coating liquid for forming the easy-adhesive layer A used for forming the easy-adhesive layer A is as follows.
(Specific cross-linking agent)
A cross-linking agent containing an epoxy group as a functional group; a cross-linking agent containing a bifunctional epoxy group (trade name; "Denacol EX-313", manufactured by Nagase ChemteX Corporation) and a tetrafunctional epoxy group. A cross-linking agent containing (trade name; "TETRAD-X", manufactured by Mitsubishi Gas Chemicals Co., Ltd.) was mixed and used at a ratio of 1: 3.
A cross-linking agent having an oxazoline group as a functional group; trade name "Epocross (registered trademark) WS-700", manufactured by Nippon Shokubai Co., Ltd.

From the results shown in Tables 1 and 2, the fiber-reinforced resin molded product according to the present invention is superior in vividness to the fiber-reinforced resin molded product of the comparative example. Further, the fiber-reinforced resin molded product according to the present invention is also excellent in adhesion.

The surface coating film according to the present invention is an epoch-making technique capable of finishing painting at the same time as being integrally molded with a fiber reinforced resin, and has excellent vividness. Therefore, only sports equipment, automobiles, ships, aircraft, etc. It can be said that it is industrially useful because it can be expanded to other uses.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on September 28, 2018 (Japanese Patent Application No. 2018-185565), the contents of which are incorporated herein by reference.

1 Surface coating film A Easy-adhesion layer A
B Base film B
b1 Easy molding layer b1
b2 flat layer b2
2 Fiber impregnated resin 3 Surface coated fiber reinforced resin molded product

Claims (11)

Base film B and
It has an easy-adhesive layer A provided on the base film B, and has.
The base film B has an easy-molding layer b1 and a flat layer b2 adjacent to the easy-adhesive layer A.
The thickness of the easy-adhesion layer A is 30 nm to 250 nm, and the thickness is 30 nm to 250 nm.
The thickness of the base film B is 50 μm to 500 μm, and the thickness is 50 μm to 500 μm.
The easily molded layer b1 and the flat layer b2 satisfy the following formulas 1 and 2, respectively.
Surface coating film for integral molding with fiber impregnated resin.
3 ≦ Ratio of the storage elastic modulus EHb2 of the flat layer b2 at 150 ° C. to the storage elastic modulus EHb1 of the easily molded layer b1 at 150 ° C. (EHb2 / EHb1) Equation 1
1000 MPa ≦ Storage elastic modulus of the easily molded layer b1 at 23 ° C. ELb1 formula 2 The surface coating film according to claim 1, wherein the EHb2 / EHb1 in the formula 1 is 50 or less. The surface coating film according to claim 1 or 2, further satisfying the following formula 3.
10 MPa ≦ Storage elastic modulus of the easily molded layer b1 at 150 ° C. EHb1 ≦ 950 MPa Formula 3 The surface coating film according to any one of claims 1 to 3, wherein the base film B is a biaxially oriented film. The surface coating film according to any one of claims 1 to 4, wherein the easily molded layer b1 and the flat layer b2 contain a thermoplastic resin. The easy-adhesion layer A includes a binder resin and
A cross-linking agent having at least one functional group selected from the group consisting of an epoxy group, an oxazoline group, a silanol group and an isocyanate group.
The surface coating film according to any one of claims 1 to 5, which comprises a cured product of the binder resin and the cross-linking agent. The surface coating film according to any one of claims 1 to 6, wherein the total light transmittance with respect to visible light is 80% or more. A surface-coated fiber-reinforced resin molded product in which a surface-coated film and a fiber-impregnated resin are integrally molded according to any one of claims 1 to 7. The surface-coated fiber-reinforced resin molded product according to claim 8, wherein the fiber-impregnated resin contains carbon fibers. Manufacture of a surface-coated fiber-reinforced resin molded product comprising a step of contacting and integrally molding the easy-adhesion layer A and the fiber-impregnated resin in the surface-coated film according to any one of claims 1 to 7. Method. The method for producing a surface-coated fiber-reinforced resin molded product according to claim 10, wherein the step is a step of integrally molding the fiber-impregnated resin at 150 ° C. for 10 minutes or less.

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